Coating compositions having chelant functionality

Field of the invention

The present invention relates to a composition for use as a floor coating having good scratch and abrasion resistance, as well as easy removability, and which comprises an aqueous solvent and a chelating polymer which comprises units derived from one or more aminocarboxylate compounds or their salts, and one or more other monomers BACKGROUND OF THE INVENTION

Floor coating compositions (e.g., polishes) are applied to flooring substrates, such as vinyl, tile or wood, to maintain a clean and sanitary appearance. They are generally intended to be sacrificial coatings which form a film that protects the underlying flooring substrate by sacrificially accepting and resisting marks, soils, scuffs, abrasion, and scratches encountered during normal use of the substrate. During its service life, the protective films must withstand rigorous maintenance practices such as aqueous detergent scrubbings and abrasive mechanical abrasion to remove, when possible, the soils, scuffs and scratches accumulated with time. When the useful or aesthetic life of the protective film has expired, it is removed from the substrate and replaced with a new coating composition. Thus, easy removability is just as important as the coating's ability to resist marks, soil, scratches, and detergents.

Past technology employed transition metal cross-linking, such as with zinc, to strike a balance between detergent resistance and removability, while maintaining the durability of the coating composition. More recently, heightened concerns regarding environmental safety have made use of zinc cross-linking technology in floor polish compositions less acceptable. Zinc can be toxic to aquatic life in streams, rivers, and lakes. Municipal sewer facilities have threshold limits on the level of zinc that enters their facilities in the waste water. Although the floor-finish industry's contribution to total zinc input may be relatively small, it remains a focus of the municipal sewer authorities. Many United States municipalities and school districts, as well as the United States Green Building Council, have begun to require the use of zinc free finishes in their custodial cleaning products and service contracts.

Zinc-free floor polish compositions developed to date tended to fall short of the expected performance characteristics by either not providing sufficient resistance to repel scuffs, soils, and scratches, or by failing to provide acceptable resistance to the detergents and mechanical rubbing employed to restore the coatings. For example, see U.S. Patent Application Publication No. 2007/0254108 which discloses floor coating compositions using calcium instead of zinc but which fail to meet industry requirements. Also, see U.S. Pat. No. 6,586,516 which discloses aqueous coating compositions comprising acetoacetate functional polymers and a divalent metal ion which may be zinc, but which is preferrably an alkaline earth metal ion, such as calcium, magnesium, or mixtures thereof. The compositions of U.S. Pat. No. 6,586,516 provide surface coatings having scuff mark resistance mar resistance and impact resistance for a variety of substrates. End-use customers would strongly prefer zinc free floor polishes that provide the performance that has come to be expected from current zinc-containing state-of-the-art floor finishes, including resistance to scuffing, marring, marking, soiling, etc. and also providing favorable removability properties.

The problem encountered when multivalent metals other than zinc, such as calcium or magnesium, are used to achieve crosslinking in floor coating compositions is that higher levels of such other metals must be used, while concurrent coating stability becomes difficult to maintain. It is also desired to incorporate other metals such as aluminum, zirconium and titanium which normally cannot be done using traditional complexing monomers (e.g., acrylic acid, methacrylic acid, itaconic acid).

Other solutions have been attempted as well. For instance, U.S. Pat. No. 5,574,090 describes an alternative to metal crosslinking in aqueous coatings systems in which a coating composition comprises a combination of a swellable polymer with a polymer which contains functionality that will interact with the swellant to facilitate stripping and removal of the coating at the end of its useful life. This patent further teaches that acid-functional polymers may be used with amine swellants and amine functional polymers may be used with acid swellants. U.S. Pat. No. 5,574,090 teaches that most preferred are polymers that contain carboxylic acid functional groups as the swellable polymers, in combination with amines such as ammonia and lower alkyl, or lower alkanol amines.

U.S. Pat. No. 5,426,142 teaches film-forming polymers which contain acetoacetate functionality and are further reacted with amino functional silane to produce self-crosslinking, ambient curing, film-forming polymers suitable for various uses including coatings and sealants for wood, glass and concrete.

More recently, it has been recognized that acrylic polymers having chelating functionality are useful for binding metal ions in various applications. For instance, U.S. Pat. No. 3,331,773 teaches preparation of water soluble polymers having chelating functionality which are useful as water treatment agents for inhibiting calcium and magnesium scale formation. These polymers are formed by grafting water soluble chelating monomers onto water soluble polymers having aliphatic polymeric backbones. Diethylenetriamine, ethylenediamine tetraacetic acid (EDTA), and other polyalkylene polyamine polyacetic acids are identified in U.S. Pat. No. 3,331,773 as examples suitable chelating monomers.

Additionally, U.S. Pat. No. 5,514,732 also describes contact lenses made from water insoluble polymers having chelating functionality. The polymers are made from aminopolycarboxylic acids with a polymerizable olefinic group, as well as a hydrophilic monomer and one or more crosslinking monomers.

U.S. Patent Application No. 2008/00262192 describes water-soluble polymers having a high chelating performance and clay dispersancy that are suitable for use as detergents, water treatment agents and dispersants. These polymers are made by polymerizing an amino group-containing allyl monomer derived from adding an amine compound, such as iminodiacetic acid (IDA), to an allyl monomer, such as allyl glycidal ether (AGE), with other polymerizable monomers including, without limitation, unsaturated monocarboxylic acid monomers.

Most recently, vinyl aminocarboxylate monomers have been found useful for providing amine-based chelating functionality. Vinyl aminocarboxylate monomers are an entire class of polymerizable acrylic monomers having amine-based chelating functionality and which are polymerizable along with ethylenically unsaturated monomers typically used to produce various types of acrylic monomers. This is related to the technology described in the aforementioned U.S. Patent Application No. 2008/00262192 where an AGE-IDA vinyl aminocarboxylate monomer is described and incorporated into carboxylic acid-based copolymers. Polymers comprising polymerized units derived from such vinyl aminocarboxylate monomers have been identified as effective chelating agents and, therefore, are expected to be useful in various possible applications. The present invention addresses the need for zinc-free floor coating compositions that provide excellent resistance to marks, soil, scratches, scuffs and detergents, while also providing superior removability characteristics for facilitating stripping at the end of the useful life of the coating. These floor coating compositions contain polymers having amine-based chelating functionality and are capable of binding metals at high loading levels to serve as an alternative to zinc-based crosslinking schemes for curing protective films.

Summary of the invention

The present invention provides a floor coating composition comprising: (A) an aqueous solvent; and (B) a chelating polymer. The chelating polymer comprises polymerized units derived from:

one or more aminocarboxylic acid compounds or their salts;

one or more polymerizable monomers comprising a vinyl group, an allyl group, or both, and optionally, an epoxy group; and

one or more ethylenically unsaturated monomers.

The polymerized units derived from (B)

one or more aminocarboxylic acid compounds or their salts comprise those having aminocarboxylic groups of at least one of the following structures:

##STR00001## wherein R.sup.1 and R.sup.2 are each, independently, hydrogen, COOX.sup.3 or COOX.sup.4; X.sup.1, X.sup.2, X.sup.3 and X.sup.4 are each, independently, hydrogen or a mono- or polyvalent cation; R.sup.3 is hydrogen or a unit derived from a polymerizable monomer; and * is the location at which the aminocarboxylic group is bound to the chelating polymer at a unit derived from a polymerizable monomer, or at a unit derived from an ethylenically unsaturated monomer.

In some embodiments, the (B)

one or more aminocarboxylic acid compounds or their salts may be selected from the group consisting of: iminodiacetic acid (IDA), iminodisuccinic acid (IDS), ethylenediamine triacetic acid (ED3A), ethylenediamine disuccinic acid (EDDS), and their salts.

Furthermore, in some embodiments, the (B)

one or more polymerizable monomers may be selected from the group consisting of: glycidyl methacrylate (GMA), allyl glycidyl ether (AGE), vinylbenzyl chloride (VBC), allyl bromide, and their derivatives.

Some embodiments of the floor coating composition comprise units derived from (B)

one or more ethylenically unsaturated monomers which are selected from the group consisting of: carboxylic acids, esters of carboxylic acids, maleic acids, styrenes, sulfonic acids, and combinations thereof.

In some embodiments, for example, the floor coating composition comprises: (A) from 1% to 95%, by weight, of the aqueous solvent, and (B) from 5% to 80%, by weight, of the chelating polymer, based on the total weight of the floor coating composition.

Furthermore, in some embodiments of the floor polish composition of the present invention, the (B) chelating polymer further comprises units derived from one or more crosslinking monomers. The crosslinking monomers may be selected from the group consisting of: divinylaromatic compounds; di-, tri- and tetra-(meth)acrylate esters; di-, tri- and tetra-allyl ether compounds, tri- and tetra-allyl ester compounds, allyl(meth)acrylate, and combinations thereof.

The present invention also provides a method for protecting a floor substrate having a surface which comprises applying, to the surface of the floor substrate, the floor coating composition comprising: (A) an aqueous solvent; and (B) a chelating polymer, as described above.

Brief description of the drawings

A more complete understanding of the present invention will be gained from the embodiments discussed hereinafter and with reference to the accompanying drawings, in which like reference numbers indicate like features, and wherein:

FIG. 1 is a plot of shear modulus (G′) vs. temperature for Comparative Examples F, G and H;

FIG. 2 is a plot of shear modulus (G′) vs. temperature for Examples 15, 3 and 9;

FIG. 3 is a plot of shear modulus (G′) vs. temperature for Example 3, Comparative Example C and Comparative Example H; and

FIG. 4 is a plot of shear modulus (G′) vs. temperature for Example 3, Example 4, Comparative Example C and Comparative Example H.

Detailed description of the invention

All percentages stated herein are weight percentages (wt %), unless otherwise indicated.

Temperatures are in degrees Celsius (° C.), and “ambient temperature” means between 20° C. and 25° C., unless specified otherwise.

As used herein, the term “(meth)acrylic” includes acrylic acid and methacrylic acid.

“Polymer” means a polymeric compound or “resin” prepared by polymerizing monomers, whether of the same or different types. Homopolymers are generally understood to be polymeric compounds which have been prepared from a single type of monomer. Similarly, copolymers are polymeric compounds prepared from at least two different types of monomers. For example, an acrylic acid polymer comprising polymerized units derived only from acrylic acid monomer is a homopolymer, while a polymer comprising polymerized units derived from acrylic acid, methacrylic acid and butyl acrylate is a copolymer. As used herein, the generic term “polymer” includes the terms “homopolymer,” “copolymer,” as well as “random” polymers and “block” polymers.

The term “polymerized units derived from” as used herein refers to polymer molecules that are synthesized according to polymerization techniques wherein a product polymer contains “polymerized units derived from” the constituent monomers which are the starting materials for the polymerization reactions. The proportions of constituent monomers, based on the total of all constituent monomers, that are used as starting materials for a polymerization reaction are assumed to result in a polymer product having the same proportions of units derived from those respective constituent monomers. For example, where 80%, by weight, of acrylic acid monomer and 20%, by weight, of methacrylic acid monomer are provided to a polymerization reaction, the resulting polymer product will comprise 80% by weight of units derived from acrylic acid and 20% by weight of units derived from methacrylic acid. This is often written in abbreviated form as 80% AA/20% MAA. Similarly, for example, where a particular polymer is said to comprise units derived from 50% by weight acrylic acid, 40% by weight methacrylic acid, and 10% by weight itaconic acid (i.e., 50% AA/40% MAA/10% IA), then the proportions of the constituent monomers provided to the polymerization reaction can be assumed to have been 50% acrylic acid, 40% methacrylic acid and 10% itaconic acid, by weight, based on the total weight of all three constituent monomers.

“Polymerizable monomers” generally means monomers or other molecule that have at least one carbon-carbon double bond and is capable of forming additional covalent bonds with other monomers or molecules of its kind, other polymerizable monomers or molecules, or polymers having polymerizable pendant groups, under normal polymerization conditions, and become incorporated in to the product polymer.

“Ethylenically unsaturated monomers” means molecules having one or more double carbon-carbon bonds, which renders them polymerizable. Monoethylenically unsaturated monomers have one carbon-carbon double bond, while multi-ethylenically unsaturated monomers have two or more carbon-carbon double bonds. As used herein, ethylenically unsaturated monomers include, without limitation, carboxylic acids, esters of carboxylic acids, maleics, styrenes and sulfonic acids. Carboxylic acid monomers include, for example, acrylic acid, methacrylic acid, and mixtures thereof. Maleic monomers include, for example, maleic acid, maleic anhydride, and substituted versions thereof. Sulfonic acid monomers include, for example, 2-(meth)acrylamido-2-methylpropanesulfonic acid, 4-styrenesulfonic acid, vinyl sulfonic acid, 2-sulfoethyl(meth)acrylic acid, 2-sulfopropyl(meth)acrylic acid, 3-sulfopropyl(meth)acrylic acid, and 4-sulfobutyl(meth)acrylic acid. Further examples of ethylenically unsaturated monomers include, without limitation, itaconic acid, crotonic acid, vinyl acetic acid, acryloxypropionic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and isobutyl methacrylate; hydroxyalkyl esters of acrylic or methacrylic acids such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate; acrylamide, methacrylamide, N-tertiary butyl acrylamide, N-methyl acrylamide, N,N-dimethyl acrylamide; acrylonitrile, methacrylonitrile, allyl alcohol, allyl sulfonic acid, allyl phosphonic acid, vinylphosphonic acid, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, phosphoethyl methacrylate, phosphonoethyl methacrylate (PEM), and sulfonoethyl methacrylate (SEM), N-vinyl pyrollidone, N-vinylformamide, N-vinylimidazole, ethylene glycol diacrylate, trimethylotpropane triacrylate, diallyl phthalate, vinyl acetate, styrene, 2-acrylamido-2-methyl propane sulfonic acid (AMPS) and its salts or combinations thereof.

The term “vinyl monomers” refers to monomers that contain a —CH═CH.sub.2 group. Examples of vinyl monomers include, but are not limited to, vinyl acetate, vinyl formamide, vinyl acetamide, vinyl pyrrolidone, vinyl caprolactam, and long chain vinyl alkanoates such as vinyl neodecanoate, and vinyl stearate.

The term “allyl monomers” refers to monomers that contain a —CH.sub.2CH═CH.sub.2 group. Examples of allyl monomers include, but are not limited to, allyl glycidyl ether (AGE), phenyl glycidyl ether, vinylbenzyl chloride (VBC), and allyl bromide.

As will be recognized by persons of ordinary skill in the relevant art, attaching a chelating compound to a polymer should provide a chelating polymer having cross linking characteristics similar to that expected from the traditionally present zinc ion—MAA/AA polymer interactions. One way this has been accomplished is by grafting chelating groups, such as amines or amine derivatives, to an acrylic polymer subsequent to the polymerization reaction which produces the acrylic polymer. See, for example, U.S. Pat. No. 3,331,773. In general, chelating compounds have the ability to form stable soluble complexes with metal ions and thus prevent their precipitation.

Chelation is characterized by the equilibrium reaction between a metal ion and the functional group of the chelating compound. The most effective chelating compounds have the capacity to bind a large number of metal ions and have a greater stability associated with the formed complex.

Chelating compounds are well known and include such compounds as amino acids and their derivatives, such as ethylenediaminetetraacetic acid (EDTA) and other polyalkylenepolyaminepolyacetic acids, including polyacids of the alkylol substituents of the polyamines. Other chelating compounds have active groups consisting of carbonyl radicals, sulfonic acid radicals, amine radicals, phosphonic acid radicals, and the like.

Applicants have discovered that polymers having chelating functionality (i.e., “chelating polymers”) where one or more aminocarboxylate-type chelating compounds have been incorporated directly into the polymer during polymerization actually provide improved performance when used in floor polish compositions compared to polymers having chelating compounds grafted onto them post-polymerization. This appears to be true regardless of whether the chelating polymers are formed by in situ polymerization of chelating compounds or their salts with particular polymerizable monomers and one or more ethylenically unsaturated monomers, or by first combining, by reaction, the chelating compounds with the particular polymerizable monomers to form polymerizable aminocarboxylic acid monomers or their salts, and then polymerizing these aminocarboxylic acid monomers or their salts with one or more ethylenically unsaturated monomers. The two methods of forming suitable chelating polymers for use in the floor polish compositions and method of the present invention will be described in further detail hereinafter.

In one embodiment, the present invention provides floor coating compositions which are zinc free and which have performance properties, such as cross-linking, gloss, and scratch resistance, which are comparable to, or better than, those of zinc-containing floor coating compositions. More particularly, the floor coating compositions of the present invention comprise: (A) an aqueous solvent; and (B) a chelating polymer comprising, as polymerized units derived from,

one or more aminocarboxylic acid compounds or their salts;

one or more polymerizable monomers comprising a vinyl group, an allyl group, or both, and, optionally, an epoxy group; and

one or more ethylenically unsaturated monomers.

In some embodiments, for example, the floor coating composition of the present invention will comprise from 1% to 95%, by weight, of the aqueous solvent, and from 5% to 80%, by weight, of the chelating polymer, based on the total weight of the floor coating composition.

For example, without limitation, the floor coating composition may comprise at least 3%, or at least 10%, or even at least 30%, by weight, of the aqueous solvent, based on the total weight of the floor coating composition. Furthermore, for example, the floor coating composition may comprise up to 70%, or up to 80%, or even up to 90%, by weight, of the aqueous solvent, based on the total weight of the floor coating composition.

In addition, the floor coating composition may, for example, without limitation, comprise at least 10%, or at least 15%, or even at least 20%, by weight, of the chelating polymer, based on the total weight of the floor coating composition. Furthermore, for example, the floor coating composition may comprise up to 65%, or up to 70%, or even up to 75%, by weight, of the chelating polymer, based on the total weight of the floor coating composition.

The aqueous solvent comprises from 5% to 95% of water, and from 1% to 50% of one or more other solvents, by weight, based on the total weight of the aqueous solvent.

In some embodiments, for example, without limitation, the aqueous solvent may comprise at least 5%, or at least 10%, or even at least 20%, by weight, of water, based on the total weight of the aqueous solvent. Also, the aqueous solvent may, for example, comprise up to up to 50%, or up to 70%, or even up to 85%, by weight, of water, based on the total weight of the aqueous solvent.

Furthermore, in some embodiments, for example, without limitation, the aqueous solvent may comprise at least 2%, or at least 5%, or even at least 10%, by weight, of the one or more other solvents, based on the total weight of the aqueous solvent. Also for example, the aqueous solvent may comprise up to up to 20%, or up to 25%, or even up to 35%, by weight, of water, based on the total weight of the aqueous solvent.

Compounds suitable for use as the one or more other solvents may, for example, be selected from coalescing solvents, plasticizing solvents, or combinations thereof. Suitable coalescing solvents, for example, may be selected from Butoxyethyl PROPASOL™, Butyl CARBITOL™, Butyl CELLOSOLVE™ Acetate, Butyl CELLOSOLVE™, Butyl DIPROPASOL™, Butyl PROPASOL™, CARBITOL™ PM-600, CARBITOL™ Low Gravity, CELLOSOLVE™ Acetate, CELLOSOLVE™, Ester EEP™, FILMER IBT™, Hexyl CARBITOL™, Hexyl CELLOSOLVE™, Methyl CARBITOL™, Methyl CELLOSOLVE™ Acetate, Methyl CELLOSOLVE™, Methyl DIPROPASOL™, Methyl PROPASOL™ Acetate, Methyl PROPASOL™, Propyl CARBITOL™, Propyl CELLOSOLVE™, Propyl DIPROPASOL™ and Propyl PROPASOL™, among others, all of which are available from Dow Chemical Company of Midland, Mich., U.S.A.

Suitable plasticizing solvents, for example, may be selected from ethylene glycol phenyl ether (commercially available as “DOWANOL™ EPh” from Dow Chemical Company), propylene glycol phenyl ether (commercially available as “DOWANOL™ PPh” from Dow Chemical Company); 2,2,4-Trimethyl-1,3-pentanediol diisobutyrate; tributoxy ethyl phosphate; dibasic esters such as dimethyl adipate, dimethyl succinate, dimethyl glutarate, dimethyl malonate, diethyl adipate, diethyl succinate, diethyl glutarate, dibutyl succinate, and dibutyl glutarate (including products commercially available under the trade designations DBE, DBE-3, DBE-4, DBE-5, DBE-6. DBE-9, DBE-IB, and DBE-ME from E.I. du Pont de Nemours and Company, of Wilmington, Del., U.S.A.); dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, and dibutyl carbonate; phthalate esters such as dibutyl phthalate, diethylhexyl phthalate, and diethyl phthalate, among others.

In the chelating polymer, the polymerized units derived from (B)

one or more aminocarboxylic acid compounds or their salts comprise those having aminocarboxylic groups of at least one of the following structures:

##STR00002## wherein R.sup.1 and R.sup.2 are each, independently, hydrogen, COOX.sup.3 or COOX.sup.4; X.sup.1, X.sup.2, X.sup.3 and X.sup.4 are each, independently, hydrogen or a mono- or polyvalent cation; R.sup.3 is hydrogen or a unit derived from a polymerizable monomer; and * is the location at which the aminocarboxylic group is bound to the chelating polymer at a unit derived from a polymerizable monomer, or at a unit derived from an ethylenically unsaturated monomer.

Suitable mono- or polyvalent cations include, without limitation, one or more of the following: Na.sup.+, K.sup.+, NH.sub.4.sup.+, Ca.sup.2+, Mg.sup.2+, Ba.sup.2+, Sr.sup.2+, V.sup.2+, Mn.sup.2+, Fe.sup.2+, Al.sup.3+, Zr.sup.2+, Co.sup.2+, Cd.sup.2+, Zn.sup.2+, TiO.sup.2+, Pb.sup.2+, Y.sup.3+, Pd.sup.2+, Ni.sup.2+, VO.sup.2+, Cu.sup.2+, Ga.sup.3+, Ti.sup.3+, Hg.sup.2+, Sc.sup.3+, Th.sup.4+, In.sup.3+, Fe.sup.3+, V.sup.3+ and combinations thereof. Preferred cations are Na.sup.+, K.sup.+, NH.sub.4.sup.+, Ca.sup.2+ and Mg.sup.2+ and combinations thereof.

Aminocarboxylic acid compounds or their salts which are suitable for use as constituent monomers of the chelating polymer include, for example, without limitation, iminodiacetic acid (IDA), iminodisuccinic acid (IDS), ethylenediamine triacetic acid (ED3A), ethylenediamine disuccinic acid (EDDS), or their salts. Of course, mixtures and combinations of different kinds of aminocarboxylic acids or their salts may be suitably included as well.

These exemplary aminocarboxylic compounds have the following pre-reaction structures:

Iminodiacetic acid (IDA), or its salt, for example, has the following general structure:

##STR00003## wherein X.sup.1 and X.sup.2 are each, independently, hydrogen or a mono- or polyvalent cation, such as those listed above.

Iminodisuccinic acid (IDS) or its salt, on the other hand, has the following general structure:

##STR00004## wherein X.sup.1, X.sup.2, X.sup.3 and X.sup.4 are each, independently, hydrogen or a mono- or polyvalent cation, such as those listed above.

Ethylenediamine triacetic acid (ED3A), or its salt, has the following general structure:

##STR00005## wherein X.sup.1, X.sup.2 and X.sup.3 are each, independently, hydrogen or a mono- or polyvalent cation, such as those listed above.

Ethylenediamine disuccinic acid (EDDS), or its salt, has the following general structure:

##STR00006## wherein X.sup.1, X.sup.2, X.sup.3 and X.sup.4 are each, independently, hydrogen or a mono- or polyvalent cation, such as those listed above.

The units of the chelating polymer which are derived from (B)

one or more polymerizable monomers comprise a vinyl group (—CH═CH.sub.2), an allyl group (—CH.sub.2CH═CH.sub.2), or both, and, optionally, an epoxy group. These units may, for example, without limitation, have one or more of the following structures:

##STR00007## ##STR00008## wherein, Y.sup.1 and Y.sup.2 are each, independently and where present, hydrogen, COOX.sup.5 or COOX.sup.6, and X.sup.5 and X.sup.6 are each, independently, hydrogen or a mono- or polyvalent cation, as defined hereinabove.

Suitable mono- or polyvalent cations include, without limitation, one or more of the following: Na.sup.+, K.sup.+, NH.sub.4.sup.+, Ca.sup.2+, Mg.sup.2+, Ba.sup.2+, Sr.sup.2+, V.sup.2+, Mn.sup.2+, Fe.sup.2+, Al.sup.3+, Zr.sup.2+, Co.sup.2+, Cd.sup.2+, Zn.sup.2+, TiO.sup.2+, Pb.sup.2+, Y.sup.3+, Pd.sup.2+, Ni.sup.2+, VO.sup.2+, Cu.sup.2+, Ga.sup.3+, Ti.sup.3+, Hg.sup.2+, Sc.sup.3+, Th.sup.4+, In.sup.3+, Fe.sup.3+, V.sup.3+ and combinations thereof. Preferred cations are Na.sup.+, K.sup.+, NH.sub.4.sup.+, Ca.sup.2+ and Mg.sup.2+ and combinations thereof.

Additionally, as will be readily recognized by persons of ordinary skill in the art relevant art, monomers suitable for deriving these units (B)

of the chelating polymer include, for example, without limitation, glycidyl methacrylate (GMA), allyl glycidyl ether (AGE), vinylbenzyl chloride (VBC), and allyl bromide, and their derivatives.

Ethylenically unsaturated monomers from which the units (B)

of the chelating polymer are derived include, without limitation, those listed hereinabove. Preferred ethylenically unsaturated monomers include carboxylic acids, esters of carboxylic acids, maleic acids, styrenes, sulfonic acids and combinations thereof.

Particularly suitable ethylenically unsaturated monomers include, for example, those containing an acidic functional group selected from one or more of carboxylic, sulfonic and phosphonic groups. For example, suitable carboxylic acid monomers include, without limitation, monoethylenically unsaturated (C.sub.3-C.sub.9) carboxylic acid monomers, such as unsaturated monocarboxylic and dicarboxylic acid monomers. For example, unsaturated monocarboxylic acids include acrylic acid (AA), methacrylic acid (MAA), alpha-ethacrylic acid, beta-dimethylacrylic acid, vinylacetic acid, allylacetic acid, ethylidineacetic acid, propylidineacetic acid, crotonic acid, acryloxypropionic acid and alkali and metal salts thereof. Suitable unsaturated dicarboxylic acid monomers include, for example, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, methylenemalonic acid and alkali and metal salts thereof.

Additional suitable monoethylenically unsaturated monomers are those containing sulfonic acid or phosphonic groups include, for example, 2-acrylamido-2-methyl-1-propane-sulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacryl-amido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 2-sulphoethyl methacrylate, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethyl acrylamide, sulfomethyl methacrylamide and phosphoethyl methacrylate.

As a further example, the one or more monoethylenically unsaturated monomers may comprise one or more (meth)acrylic monomers containing one or more pendant reactive functional groups selected from hydroxy, thiol, and amino groups. Suitable hydroxy-functional (meth)acrylic monomers include, for example, hydroxyl (C.sub.1-C.sub.4)alkyl(meth)acrylates, such as hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate and hydroxypropyl acrylate. Suitable amino-functional (meth)acrylic monomers include, for example, dimethylaminopropyl methacrylamide, dimethylaminopropyl acrylamide, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethyl-aminopropyl methacrylate and dimethylaminopropyl acrylate. Suitable thiol-functional (meth)acrylic monomers include, for example, 2-mercaptopropyl methacrylate.

As a still further example, the one or more monoethylenically unsaturated monomers may comprise one or more (C.sub.1-C.sub.20)alkyl(meth)acrylate ester monomers, such as, without limitation, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, secondary butyl acrylate, tertiary-butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, cyclopropyl, methacrylate, butyl methacrylate and isobutyl methacrylate, hexyl and cyclohexyl methacrylate, cyclohexyl acrylate, isobornyl methacrylate, 2-ethylhexyl acrylate (EHA), 2-ethylhexyl methacrylate, octyl(meth)acrylate, decyl(meth)acrylate, isodecyl(meth)acrylate, undecyl(meth)acrylate, dodecyl(meth)acrylate (also known as lauryl(meth)acrylate), tridecyl(meth)acrylate, tetradecyl(meth)acrylate (also known as myristyl(meth)acrylate), pentadecyl(meth)acrylate, hexadecyl(meth)acrylate (also known as cetyl(meth)acrylate), heptadecyl(meth)acrylate, octadecyl(meth)acrylate (also known as stearyl(meth)acrylate), nonadecyl(meth)acrylate, eicosyl(meth)acrylate and combinations thereof. Typically, the (C.sub.1-C.sub.20)alkyl(meth)acrylate esters are (C.sub.1-C.sub.8)alkyl(meth)acrylate esters and preferably (C.sub.1-C.sub.8)alkyl acrylate esters; more preferably, the (C.sub.1-C.sub.20)alkyl(meth)acrylate esters are selected from methyl acrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate; most preferably, the acrylate esters are selected from butyl acrylate and 2-ethylhexyl acrylate.

The one or more monoethylenically unsaturated monomers used to prepare the water insoluble polymer binders, may comprise one or more vinylaromatic monomers, such as, for example, styrene, alpha-methyl styrene and substituted styrenes, such as vinyl toluene, 2-bromostyrene, 4-chlorostyrene, 2-methoxystyrene, 4-methoxystyrene, alpha-cyanostyrene, allyl phenyl ether and allyl tolyl ether.

It is also possible for the water insoluble polymer resins to comprise, as polymerized units, 0-50%, such as 0-25%, of one or more other copolymerizable monomers. Suitable other copolymerizable monomers include, for example, butadiene, acrylonitrile, methacrylonitrile, crotononitrile, alpha-chloroacrylonitrile, ethyl vinyl ether, isopropyl vinyl ether, isobutyl vinyl ether, butyl vinyl ether, diethylene glycol vinyl ether, decyl vinyl ether, ethylene, methyl vinyl thioether and propyl vinyl thioether, esters of vinyl alcohol, and amides of ethylenically unsaturated (C.sub.3-C.sub.6)carboxylic acids, amides of ethylenically unsaturated (C.sub.3-C.sub.6)carboxylic acids that are substituted at the nitrogen by one or two (C.sub.1-C.sub.4)alkyl groups, acrylamide, methacrylamide and N-methylol(meth)acryl-amide.

The constituent monomers, (B)(1), (B)

and (B)(3), from which the chelating polymer is derived may, for example, be provided individually, or in various mixtures, to the polymerization reaction process which produces the chelating polymer. This is referred to herein as the “in situ” method of preparing the chelating polymer, i.e., where all three categories of constituent monomers are supplied and polymerized together.

Alternatively, the chelating polymer may be produced by providing a polymerizable aminocarboxylic acid monomer or its salt, which is the reaction product of the (B)

one or more aminocarboxylaic acid compounds or their salts and the (B)

one or more polymerizable monomer, to the polymerization reaction, along with the (B)

one or more ethylenically unsaturated monomers. In other words, the one or more polymerizable monomers comprising a vinyl group, an allyl group, or both, and optionally an epoxy group are first modified by reacting with (B)

one or more aminocarboxylaic acid compounds or their salts, thereby forming polymerizable aminocarboxylic acid monomers or their salts. The polymerizable aminocarboxylic acid monomers or their salts are then polymerized with one or more ethylenically unsaturated monomers to produce the chelating polymers suitable for use in the floor polish compositions and method of the present application.

In some embodiments, for example, polymerizable aminocarboxylic acid monomers or their salts are prepared from a polymerizable monomer and at least one chelating compound selected from the group consisting of: iminodiacetic acid; iminodisuccinic acid; ethylenediamine triacetic acid; and ethylenediamine disuccinic acid. In such embodiments, the one or more polymerizable monomers may, for example without limitation, be glycidyl methacrylate (GMA), allyl ether (AGE), vinylbenzyl chloride (VBC) or mixtures thereof. The resulting polymerizable aminocarboxylic acid monomers or their salts are then polymerized with one or more ethylenically unsaturated monomers. Preferred ethylenically unsaturated monomers include: butyl acrylate (BA), methyl methacrylate (MMA), methacrylic acid (MAA), itaconic acid (IA), styrene (STY), and their salts and derivatives.

Furthermore, in some embodiments, the chelating polymer (B) in the floor coating composition comprises

from 1% to 99%, by weight of the one or more vinyl aminocarboxylic acid monomers; and

from 1% to 99%, by weight of the one or more ethylenically unsaturated monomers, based on the total weight of the chelating polymer (B).

In some embodiments of the floor polish composition according to the present invention, the chelating polymer may further comprise units derived from

one or more crosslinking monomers. Crosslinking monomers are monomers having two or more ethylenically unsaturated groups, and may include, for example, without limitation, divinylaromatic compounds, di-, tri- and tetra-(meth)acrylate esters, di-, tri- and tetra-allyl ether or ester compounds and allyl(meth)acrylate. Preferred crosslinking monomers for use in the present invention include, for example, divinylbenzene (DVB), trimethylolpropane diallyl ether, tetraallyl pentaerythritol, triallyl pentaerythritol, diallyl pentaerythritol, diallyl phthalate, diallyl maleate, triallyl cyanurate, bisphenol A diallyl ether, allyl sucroses, methylene bisacrylamide, trimethylolpropane triacrylate, allyl methacrylate (ALMA), ethylene glycol dimethacrylate (EGDMA), hexane-1,6-diol diacrylate (HDDA) and butylene glycol dimethacrylate (BGDMA). Especially preferred crosslinking monomers include DVB, ALMA, EGDMA, HDDA and BGDMA. When present in some embodiments, the one or more crosslinking monomers may be bi-, tri-, or tetra-ethylenically unsaturated, or even a combination thereof.

The chelating polymer may comprise from 0.3% to 3% of units derived from one or more crosslinking monomers, by weight, based on the total weight of the chelating polymer. For example, in some embodiments, the chelating polymer may comprise at least 0.4%, or at least 0.6%, or at least 0.8%, or at least 0.9%, or even at least 1.1%, by weight, based on the total weight of the chelating polymer. Similarly, For example, in some embodiments, the chelating polymer may comprise up to 2.8%, or up to 2.5%, or up to 2.1%, or up to 1.8%, or even up to 1.5%, by weight, based on the total weight of the chelating polymer.

Copolymerizing polymerizable aminocarboxylic acid monomers or their salts with traditional ethylenically unsaturated monomers, such as butyl acrylate (BA), methyl methacrylate (MMA), methacrylic acid (MAA), itaconic acid (IA), and styrene (STY) produces unique aqueous emulsion compositions comprising chelating polymers (B) that are capable of binding metals at high loading levels and, therefore, suitable for use in zinc-free floor coating compositions which have the desired degree of resistance to marks, soil, scratches, and detergents, as well as easy removability when the coating is to be replaced with a new one.

Specifically, applicants have found that the presence of the aminocarboxylate groups from the one or more vinyl aminocarboxylic acid monomers improves the calcium binding ability of traditional floor care polymers. The polymerizable chelant monomers prepared and evaluated included vinyl aminocarboxylate monomers based on the reaction of iminodiacetic acid (IDA) or ethylenediaminetriacetic acid (ED3A) (i.e., amine compounds) with glycidyl methacrylate (GMA), allyl ether (AGE) or vinylbenzyl chloride (VBC), or their derivatives (i.e., traditional vinyl monomers).

As evidenced by the data provided in the examples hereinbelow, test results confirmed improved calcium incorporation with improved calcium cross-linking properties for chelant based copolymers compared to traditional polymer compositions which did not contain the new aminocarboxylate groups. The chelant-based polymers provided gloss performance in floor polish that is comparable to the conventional floor polishes. Additionally, the chelant polymers showed scratch resistance properties that were superior to the conventional floor polish.

The description continues in the full USPTO document.